US20220364224A1 - Diamond and preparation method and application thereof - Google Patents
Diamond and preparation method and application thereof Download PDFInfo
- Publication number
- US20220364224A1 US20220364224A1 US17/292,001 US202117292001A US2022364224A1 US 20220364224 A1 US20220364224 A1 US 20220364224A1 US 202117292001 A US202117292001 A US 202117292001A US 2022364224 A1 US2022364224 A1 US 2022364224A1
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- Prior art keywords
- diamond
- deposition
- plasma
- coupling
- gas
- Prior art date
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Links
- 239000010432 diamond Substances 0.000 title claims abstract description 233
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 226
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 239000000463 material Substances 0.000 claims abstract description 74
- 230000006911 nucleation Effects 0.000 claims abstract description 73
- 238000010899 nucleation Methods 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 71
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 35
- 238000005520 cutting process Methods 0.000 claims abstract description 27
- 238000012545 processing Methods 0.000 claims abstract description 27
- 238000012805 post-processing Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 186
- 230000008021 deposition Effects 0.000 claims description 181
- 239000007789 gas Substances 0.000 claims description 113
- 230000008878 coupling Effects 0.000 claims description 65
- 238000010168 coupling process Methods 0.000 claims description 65
- 238000005859 coupling reaction Methods 0.000 claims description 65
- 238000005530 etching Methods 0.000 claims description 48
- 238000000227 grinding Methods 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001020 plasma etching Methods 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- 238000003698 laser cutting Methods 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 7
- 238000000295 emission spectrum Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009529 body temperature measurement Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000003746 surface roughness Effects 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012993 chemical processing Methods 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002231 Czochralski process Methods 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 51
- 239000010408 film Substances 0.000 description 41
- 230000008569 process Effects 0.000 description 17
- 230000035882 stress Effects 0.000 description 12
- 230000005284 excitation Effects 0.000 description 9
- 238000001755 magnetron sputter deposition Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 8
- 238000005137 deposition process Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 229910001018 Cast iron Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007667 floating Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- -1 copper Chemical compound 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
- C23C16/0263—Irradiation with laser or particle beam
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/274—Diamond only using microwave discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/279—Diamond only control of diamond crystallography
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32055—Arc discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32321—Discharge generated by other radiation
- H01J37/32339—Discharge generated by other radiation using electromagnetic radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32357—Generation remote from the workpiece, e.g. down-stream
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3266—Magnetic control means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3266—Magnetic control means
- H01J37/32669—Particular magnets or magnet arrangements for controlling the discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3266—Magnetic control means
- H01J37/32678—Electron cyclotron resonance
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
- H01L29/1602—Diamond
Definitions
- the present disclosure relates to the field of preparation of superhard materials, and specifically relates to a high-quality diamond and a preparation method and application thereof.
- Diamonds have many excellent properties, such as the highest hardness, the best wear resistance, etc., which makes diamonds have a wide range of uses in many aspects.
- the main preparation methods include high-temperature and high-pressure method, explosion method, chemical vapor deposition method and so on.
- the explosion method can only produce powder, while the conditions for the high-temperature and high-pressure method are relatively harsh, and the purity of the prepared diamond is low.
- plasma chemical vapor deposition method is becoming widerly, and can be used to prepare diamond coating tools, crystal diamond, free standing optical window, etc.
- the main industrial methods include hot filament, microwave, arc torch, magnetron sputtering, etc.
- the hot filament method is low cost, but the quality of the diamond is not high, while the microwave method is of high quality, but the equipment is complicated, and it is difficult to scale up production and costs; the arc torch method can produce high-quality single crystal optical-grade diamond, but the internal stress of the diamond is relatively high, the cost is relatively high, and the product is less than 80%.
- the present disclosure is intended to overcome the deficiencies of the prior art, and to provide an improved preparation method for diamond, which can stably obtain high-quality diamonds.
- the present disclosure further provides a diamond prepared according to the above-mentioned method at the same time.
- the present disclosure further provides use of the diamond prepared above-mentioned in the preparation of cutting tools and heat sinks at the same time.
- a method for preparing diamond comprises the following steps in sequence:
- Way I using a first material as the substrate material, performing surface polished processing, and forming a first nucleation layer on a surface of the substrate material to obtain the substrate holder, the first material being a material that does not react with carbon at the vapor deposition temperature of diamond, and the material of the first nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- Way II using a second material as the substrate material, performing surface polished processing, and forming a second nucleation layer to obtain the substrate holder, the second material being a material that softens or melts at the vapor deposition temperature of diamond, and the material of the second nucleation layer is selected from carbon, silicon, silicon carbide, silicon nitride, and combinations thereof;
- a material of the loose layer is selected from amorphous carbon, amorphous silicon, diamond micro-powder, silica micro-powder, aluminum oxide micro-powder, and combinations thereof;
- a material of the third nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- the plasma chemical vapor deposition method uses a multi-energy sources to couple with plasma, and the plurality of energy sources are 2, 3, or more kinds;
- the first material may be specifically selected from materials that do not react with carbon, such as copper, copper alloy, silicon carbide, aluminum oxide, silicon dioxide, and microcrystalline glass ceramics.
- the second material may be selected from mercury, plumbum, tin, aluminum, sodium, and alloys thereof, etc.
- the substrate material is not particularly limited, and may be any suitable material, specifically, it may be selected from those materials that react with diamond at the vapor deposition temperature of diamond, or may be selected from the first material and the second material mentioned above.
- the substrate material is selected from those materials that react with diamond at the vapor deposition temperature of diamond, specifically, for example, iron, iron alloy, nickel, nickel alloy, titanium, tungsten, molybdenum and alloys thereof, etc.
- the first nucleation layer may have a thickness of 5 nm-5 ⁇ m, and the existence of the first nucleation layer is very helpful for the growth of diamond in the subsequent steps and greatly improves its growth efficiency.
- the nucleation density of the first nucleation layer is not particularly limited, but from an industrial point of view, it is preferably not lower than 1.0 ⁇ 10 13 per cm 2 .
- the thickness of the first nucleation layer may more preferably be 50 nm-500 nm.
- the second nucleation layer has a thickness of 200 nm-5 ⁇ m, and the provision of the second nucleation layer can effectively ensure the overall structure and integrity of the finally formed and separated diamond film.
- the nucleation density of the second nucleation layer is also not particularly limited, but from an industrial point of view, it is preferably not lower than 1.0 ⁇ 10 13 per cm 2 .
- the thickness of the second nucleation layer may more preferably be 500 nm-5 ⁇ m, and even more preferably be 1-5 ⁇ m.
- the loose layer has a thickness of 0.01 nm-1000 ⁇ m, and the function of the loose layer is to facilitate the separation of the formed diamond film from the substrate holder and at the same time facilitate the diamond nucleation, in terms of its function, there is no special requirement for its specific thickness if it is suitable for practical industrial production.
- the substrate holder adopting Way III is particularly suitable for obtaining a self-supporting diamond thick film with perfect crystal form.
- the material of the loose layer is not limited to those mentioned above, and may also be other materials having a crystal structure similar to that of diamond.
- the loose layer may be a loose layer in the initial stage, or it may be formed by vaporized and decomposed during the diamond deposition process.
- the third nucleation layer has the same function as the first nucleation layer, which is to promote the deposition and growth of diamond, and its thickness may be 0.1 nm-100 ⁇ m, and the nucleation density is not lower than 1 ⁇ 10 13 per cm 2 .
- the loose layer can be prepared using processes known in the art such as chemical vapor deposition, thermal deposition, spin coating, or Czochralski method.
- the first nucleation layer, the second nucleation layer, and the third nucleation layer may be respectively formed using a chemical vapor deposition method.
- the surface of the substrate holder is a nano-level plane, a micron-level plane or a millimeter-level plane.
- the surface finish of the nano-level plane is 0.1-1000 nm
- the surface finish of the micron-level plane is 0.1-1000 ⁇ m
- the surface finish of the millimeter-level plane is 0.1-1000 mm.
- the surface finish of the nano-level plane is 0.1-500 nm
- the surface finish of the micron-level plane is 10-800 ⁇ m
- the surface finish of the millimeter-level plane is 1-1000 mm.
- the surface finish of the nano-level plane is 1-500 nm
- the surface finish of the micron-level plane is 50-800 ⁇ m
- the surface finish of the millimeter-level plane is 100-1000 mm.
- the surface of the substrate holder is a nano-level plane.
- the temperature of the substrate holder is preferably from room temperature to 1200° C., further preferably 500-1200° C., and still further preferably 800-1000° C.
- the deposition pressure is generally 0.01 to 200 kPa, preferably 0.1 to 20 kPa, further preferably 1 to 10 kPa, and still further preferably 2 to kPa.
- the speed of depositing diamond may be controlled between 0.01-1000 ⁇ m/h, but from the perspective of ensuring the quality of diamond, preferably, the speed is controlled to 0.01-200 ⁇ m/h, and further preferably, the speed is controlled to 0.1-100 ⁇ m/h. Still further preferably, the speed is controlled to 1-50 ⁇ m/h.
- the deposition gas is a mixture of an etching gas, a diamond carbon source gas, an assisted deposition or doping gas.
- the etching gas is selected from hydrogen, ammonia, fluorine, hydrogen fluoride, hydrogen chloride, and combinations thereof
- the diamond carbon source gas is selected from methane, acetone, acetylene, and combinations thereof.
- the assisted deposition or doping gas is selected from nitrogen, argon, xenon, borane, silane, phosphorane, and combinations thereof.
- a purity of each gas in the deposition gas is not less than 99.9999%.
- the energy sources are selected from magnetic resonance, electric arc, hot filament, flame, microwave, radio frequency, high frequency, direct current, laser, ion beam, electron beam, electron cyclotron resonance, and also meet the following (i) or (ii):
- the plurality of energy sources comprises at least magnetic resonance, and the energy of the plasma in the diamond deposition area is equalized through a coupling of the plurality of energy sources;
- the plurality of energy sources does not comprise magnetic resonance, when performing the plasma chemical vapor deposition, magnetic confinement is applied to shield more than 99.9% of energy ions above 5 keV from the diamond deposition area;
- the plasma density in the diamond deposition area is controlled to be (0.1-100) ⁇ 10 10 per cm 3 .
- the electric arc may be a cathode arc or an arc torch.
- the coupling of the plurality of energy sources adopts one of the following coupling modes:
- Mode A the coupling of the plurality of energy sources is the coupling of laser and/or microwave, cathode arc, electron cyclotron resonance;
- Mode B the coupling of the plurality of energy sources is the coupling of arc torch, magnetic resonance and electron cyclotron resonance;
- Mode C the coupling of the plurality of energy sources is the coupling of magnetic resonance, hot filament and direct current
- Mode D the coupling of the plurality of energy sources is the coupling of magnetic resonance, hot filament and high frequency
- the laser and/or microwave are first coupled with the cathode arc to smoothly initiate the cathode arc sustainably and stably generate the cathode arc, and after the generated plasma excited by the cathode arc passes through the magnetic confinement to shield high-energy ions (ions with energy higher than 5 keV), it couples with the electron cyclotron resonance plasma.
- the plasma generated by the arc torch is first coupled with the magnetic resonance plasma, and through the coupling, at a position of 10-15 mm from the arc torch mouth, a temperature gradient from a torch core to a torch edge is 40 to 50 degrees Celsius/mm.
- the internal thermal stress of the formed diamond film layer is less than 200 MPa.
- the thermal stress inside the prepared diamond is above 1 G, and the growth area of the diamond is only a tube conical area of 3-5 mm from the arc edge), the effect of coupling is very significant.
- the diamond deposition rate may reach 40-50 ⁇ m/h through coupling, and the hardness of the obtained diamond film reaches 80-100 GPa.
- the plasma density in the diamond deposition area is 0.1 ⁇ 10 10 -10 ⁇ 10 10 per cm 3 , and further preferably, the plasma density in the diamond deposition area is 0.1 ⁇ 10 10 -1 ⁇ 10 10 per cm 3 .
- a diamond deposition area with a distance of 5-100 mm from the hot filament is obtained (while only the hot filament is used as an energy source, the effective diamond deposition area is a tubular area of 3-5 mm from the hot filament).
- Mode D when the diamond deposition rate reaches 40-50 ⁇ m/h through coupling, the hardness of the obtained diamond film reaches 80-100 GPa.
- the hardness of the obtained diamond can only reach 30-70 GPa when the deposition rate is 2-5 ⁇ m/h. If the deposition rate is further increased, the hardness of the diamond will further decrease.
- Step (2) the environment or conditions of chemical vapor deposition are balance controlled, and the environment or conditions are one or more of deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow rate.
- the specific control method can be conventional means known in the art.
- the photoelectric self-feedback control system comprises a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation is not higher than 0.5° C., the deposition voltage deviation is not higher than 0.5 V the deposition current deviation is not higher than 0.5 A, the deposition power deviation is not higher than 10 W, the deposition gas pressure deviation is not higher than 50 Pa, and the deposition gas flow deviation is not higher than 0.5 sccm.
- the temperature difference range of the substrate holder is controlled to be less than 0.5° C., and materials with different thermal conduction rates are padded between the substrate holder and a heat dissipation water-cooling cavity, such as graphite, copper, stainless steel, and foamed alumina, to control the thermal conduction rate, the temperature gradient of the base of the substrate holder, and the cooling rate, to improve the quality of diamond deposition, and to reduce the temperature difference stress of diamond.
- a heat dissipation water-cooling cavity such as graphite, copper, stainless steel, and foamed alumina
- Step (2) it is also preferable to control the temperature gradient and the energy transfer direction of the temperature field in the diamond deposition area to control the deposition of diamond, as desired.
- the post-processing preferably comprises chemical processing, plasma etching, cutting, grinding and polishing carried out in sequence.
- the post-processing comprises cutting and grinding and polishing carried out in sequence.
- Step (3) the chemical processing is processing with an organic acid and/or an inorganic acid, or a combination thereof with hydrogen peroxide;
- the cutting is laser cutting
- the laser has a wavelength of 100-1100 nm, a laser power of 0.1-100 kW, and a repetition rate of 0.1-99.9%, and the surface roughness after cutting is 0.1 nm-100 ⁇ m;
- the laser cutting is pulsed laser cutting, when used for cutting diamond, by controlling the overlap rate between the spots generated by two adjacent pulsed lasers, and combined with the control of the laser spot diameter, it can be realized that the diamond after processed can achieve the desired ideal surface finish, therefore, the aforementioned “repetition rate of 0.1-99.9%” means that the overlap rate between the spots generated by two adjacent pulsed lasers is 0.1-99.9%.
- the grinding and polishing is mechanical grinding. Further, a gyration accuracy of the grinding spindle is less than 50 nm, the vibration amplitude of the grinding disc is less than 50 nm, and the grinding paste is diamond grinding paste; the grinding disc is a phosphorous cast iron grinding disc with a rotation speed of 0.1-300,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer is not less than 50 nm;
- the etching gas is composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:0.1-100:0.1-100;
- the energy source is direct current glow plasma, the etching gas pressure is 0.1-100 kPa, the etching time is 30 s-120 min, and the etching depth is 50-100 nm.
- the preparation method further comprises a repair step performed after Step (3), and the repair step is plasma chemical vapor deposition and/or plasma etching, and in the plasma chemical vapor deposition, the deposition gas is composed of methane, hydrogen and argon with a volume ratio of 1:(0.1-200):(0.1-100); the deposition pressure is 0.1-100 kPa, the deposition time is 1 min-120 min, and the deposition thickness is 0.1-100 nm.
- the repair step is plasma chemical vapor deposition and/or plasma etching, and in the plasma chemical vapor deposition, the deposition gas is composed of methane, hydrogen and argon with a volume ratio of 1:(0.1-200):(0.1-100); the deposition pressure is 0.1-100 kPa, the deposition time is 1 min-120 min, and the deposition thickness is 0.1-100 nm.
- the obtained diamond has the following characteristics:
- the exposed microscopic surface is selected from (111) crystal faces, (100) crystal faces, (110) crystal faces, amorphous crystal faces, and combinations thereof, and the size of the exposed microscopic crystal form is nano level (may be 0.1-1000 nm), micron level (may be 0.1-1000 ⁇ m) or millimeter level (may be 0.1-1000 mm);
- Its structure is single crystal, nanocrystal, microcrystal, columnar crystal, or a combination of various crystal indefinite laminates, the thickness of the laminates is 0.1 nm-1000 ⁇ m, and the number of laminated layers is two, three or more, and the number of layers is not limited:
- the carbon content of its sp 3 structure is 80-100%.
- Another technical solution provided by the present disclosure is, a diamond prepared according to the above-mentioned method.
- the diamond has good toughness, impact resistance and long service life.
- Another technical solution provided by the present disclosure is, use of the diamond above-mentioned in the preparation of cutting tools and heat sinks.
- the preparation method proposed by the present disclosure comprehensively designs the whole process, especially by processing of the substrate material of the substrate holder in the early stage, the coupling of the plurality of energy sources in the deposition process, and specific post-processing, the preparation of a stable and uniform diamond film is achieved.
- the diamond film obtained by the method of the present disclosure especially the diamond thick film, has good toughness, impact resistance and long service life.
- the method of the present disclosure has low cost, high production efficiency and good stability, and is suitable for large-scale diamond production of high-quality large-area diamond films.
- FIGS. 1 to 4 show the designs of the respective energy sources in a plurality of energy source coupling Modes A, B, C, and D in sequence:
- FIG. 5 is an SEM image of the diamond made in Embodiment 1 of the present disclosure:
- FIG. 6 is an SEM image of the diamond made in Embodiment 2 of the present disclosure.
- FIG. 7 is an SEM image of the diamond made in Embodiment 3 of the present disclosure.
- FIG. 8 is an SEM image of the diamond made in Embodiment 4 of the present disclosure.
- 11 arc cathode
- 12 arc anode
- 13 microwave feed inlet
- 14 laser feed inlet
- 15 magnetic mirror coil
- 16 first electron cyclotron coil
- 17 first deposition area
- 18 first deposition chamber
- 21 arc torch inlet
- 22 equalizing magnetic field coil
- 23 second electron cyclotron coil
- 24 second deposition area
- 25 second deposition chamber
- 31 pulse electrode
- 32 first hot filament
- 33 first coupling coil
- 34 deposition substrate holder
- 35 third deposition chamber
- 41 second coupling coil
- 42 second hot filament
- 43 high frequency
- 44 upper deposition substrate holder
- 45 lower deposition substrate holder
- 46 fourth deposition chamber.
- the fine processing of the substrate holder facilitates the stripping of the diamond, reduces the stress of the diamond, and obtains high-quality diamonds.
- Way I using a first material as the substrate material, performing surface polished processing, and forming a first nucleation layer on a surface of the substrate material to obtain the substrate holder, the first material being a material that does not react with carbon at the vapor deposition temperature of diamond, and the material of the first nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- Way II using a second material as a substrate material, performing surface polished processing, and forming a second nucleation layer to obtain the substrate holder, the second material being a material that softens or melts at the vapor deposition temperature of diamond, and the material of the second nucleation layer is selected from carbon, silicon, silicon carbide, silicon nitride, and combinations thereof;
- Way III processing the surface of the substrate material and forming a loose layer and a third nucleation layer thereon in sequence to serve as a substrate holder
- the material of the loose layer is selected from the group consisting of amorphous carbon, amorphous silicon, diamond micro-powder, silica micro-powder, aluminum oxide micro-powder, and combinations thereof
- the material of the third nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof.
- the substrate holders processed or prepared according to the above three schemes are not only very conducive to the growth of the diamond film, but also easy to separate from the diamond film after the diamond film is formed in the later stage, ensuring that a diamond with complete and large area is obtained.
- the present disclosure further obtains plasma that is most conducive to diamond formation through the coupling of a plurality of energy sources, obtaining high-quality diamonds with higher efficiency, and reducing energy consumption while improving diamond preparation efficiency.
- the energy density of a single hot filament, microwave, and arc torch is limited to 500 W per square millimeter or less, and through the coupling of a plurality of energy sources, the energy density can be significantly increased, for example, the use of a regular pentagonal cavity structure to design a microwave resonant cavity, can increase the energy density of microwave plasma by five times; the coupling of hot filament and electric arc process can increase the energy density by more than two times.
- the coupling of multiple energy sources is not a single energy superposition.
- the purpose of coupling a plurality of energy sources is to use more energy to generate effective excitation ionization, and increase the number and proportion of the deposited diamond CH 2 groups (since the ionized ion energy is not the higher the better, the generation and recombination of free ions requires specific energy level transitions and frequencies and free paths
- the coupling of a plurality of energy sources of the present disclosure can fit the feed-in energy with the characteristic spectrum, frequency, and free path of the plasma, to generate resonance or excitation, and promote effective excitation ionization, while the simple superposition of a plurality of energy sources is an ineffective superposition, which only generates excess light and heat, causes excess heat transfer and special requirements for materials and equipment structure, but is not beneficial to the energy density of the diamond production area). It increases the effective energy consumption at the same power by 20-30 times; that is, at the same power, the deposition speed of the
- the hot filament is a linear energy source
- the microwave is a spherical energy source
- the arc torch is a point-like energy source
- the suitable areas for diamond growth are a tubular area 3-5 mm from the hot filament, and a spherical shell area 3-5 mm from the standing microwave, and a tube cone-shaped area 3-5 mm from the arc edge.
- a single energy source can only form a very small confined diamond deposition growth area, and through the coupling of a plurality of energy sources, a specific uniform area can be stretched, and the plasma area for effective diamond growth can be stretched by 5-100 mm:
- the core areas of plasmas of hot filament, microwave, and electric arc have large amounts of high-energy plasmas, especially ions with energy higher than 5 keV. These ions are useless for diamond deposition but can graphitize the diamond that has been prepared and reduce the quality of the diamond.
- the plasma energy can be balanced to the greatest extent and high-energy ions can be effectively reduced; by applying magnetic confinement, more than 99.9%, further, more than 99.99%, and still further, more than 99.999% of high-energy ions (50 keV) are shielded from the diamond deposition area.
- Various energy sources comprise cathode arc, electron cyclotron resonance, and optional microwaves and lasers.
- a voltage is applied between an arc cathode 11 and an arc anode 12 , and the voltage is not enough to be in a discharge state, and microwave and laser are fed through a microwave inlet 13 and a laser inlet 14 respectively, or only one of them is fed, through their excitation, the plasma arc ignition is generated, so that a smooth discharge is generated between the arc anode 12 and the arc cathode 11 and the discharge continues steadily.
- the cathode is a high-purity carbon target.
- the generated plasma removes large particles and high-energy ions through the magnetic confinement effect of a magnetic mirror coil 15 , and at the same time, under the condition of the electron cyclotron magnetic field formed by a first electron cyclotron coil 16 , only hydrogen ions and carbon ions suitable for diamond growth reach a first deposition area 17 of a first deposition chamber 18 , thereby obtaining high-quality diamonds.
- the employed plurality of energy sources comprises arc torch, magnetic resonance and electron cyclotron resonance.
- the arc torch After the arc torch is ejected from the arc torch mouth, it enters the cavity from an arc torch inlet 21 and uses an equalizing magnetic field coil 22 to apply a primary magnetic resonance (equalizing magnetic field) to force the center temperature and high-energy ions of the arc torch to deflect and collide with the ions on the edge of the arc torch to generate exchange.
- the temperature gradient is reduced from 2000-4000 degrees Celsius/mm at the arc torch outlet to 400-500 degrees Celsius/mm, and further homogenizes under the condition of the electron cyclotron magnetic field formed by a second electron cyclotron coil 23 to charge the central ion by collision, and through the control of distance and magnetic field, the temperature gradient at the position of 10-15 mm from the mouth of the arc torch is further reduced from 400-500 degrees Celsius/mm to 40-50 degrees Celsius/mm, and at the same time, high-energy particles greater than 5 keV are deflected by a magnetic field and collide and couple to reduce to less than 5 keV.
- the energy of the plasma in a second deposition area 24 in a second deposition chamber 25 is equalized, and by controlling the frequency and size of the precisely coupled magnetic field, the proportion of ions producing diamond is oriented to increase.
- the employed plurality of energy sources is magnetic resonance (specifically, magnetic cyclotron resonance), hot filament and direct current.
- a pulse electrode 31 that is, a pulsed direct current bias power source, is applied between a first hot filament 32 and a deposition substrate holder 34 , and a first coupling coil 33 is used to apply a magnetic cyclotron resonance magnetic field around the deposition substrate holder 34 .
- the employed plurality of energy sources is magnetic resonance (specifically, magnetic cyclotron resonance), hot filament and high frequency.
- An upper deposition substrate holder 44 and a lower deposition substrate table 45 are respectively arranged on two parallel sides of a second hot wire 42 to produce diamonds.
- High frequency 43 is used to generate a high frequency discharge between the two substrate holders.
- a magnetic cyclotron resonance magnetic field is applied around the lower deposition substrate holder 45 using a second coupling coil 41 . By controlling the size and changing direction of the magnetic field, the density and uniformity of plasma on the surface of the substrate holder are increased.
- the present disclosure further improves the toughness and impact resistance of the diamond and improves the service life of the diamond.
- the multi-mode closed-loop control technology may be used in the vapor deposition process of diamond, to realize the balance control of the key environment, conditions and temperature field of the deposition, reduce manual operation error, and improve the quality and stability of production.
- the method of the present disclosure is also applicable to the production processes of plasma chemical vapor deposition thin film coated cutting tools, single crystal diamond, polycrystalline optical-grade diamond, etc., and can also be expected to obtain the desired effect.
- the high-quality diamond self-supporting thick film prepared by the method of the present disclosure is expected to greatly reduce the preparation cost of diamond thick film cutting tools, and improve processing quality, and it can also be applied to the field of heat sinks.
- This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2 mm), and comprises the following steps in sequence.
- the processing of the substrate holder was carried out according to Way III of the present disclosure, and comprised the following steps in sequence:
- a loose layer (with a thickness of 5 ⁇ m) was formed on the surface of the titanium substrate, and the process was: depositing the loose carbon film on the titanium surface by vapor deposition, and in the deposition process, the power was 5 kW, the deposition time was 20 min, and the gas was high-purity methane:
- the diamond film layer was the coupling of five energy sources, namely electric arc, electron cyclotron resonance, magnetic resonance, laser and microwave, and the specific coupling mode was the aforementioned Mode A, the plasma density in the diamond deposition growth area was controlled to be 1 ⁇ 10 10 per cm 3 ;
- the deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- the temperature of the substrate holder was controlled to 900° C.
- the deposition pressure was controlled to 5 kPa
- the diamond deposition speed was controlled to 8 ⁇ m/h.
- the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process
- the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system
- the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C.
- the deposition voltage deviation was not higher than 0.5 V
- the deposition current deviation was not higher than 0.5 A
- the deposition power deviation was not higher than 10 W
- the deposition gas pressure deviation was not higher than 50 Pa
- the deposition gas flow deviation was not higher than 0.5 sccm
- the post-processing comprised the following steps in sequence:
- Plasma etching the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 ⁇ m; silicon and the nucleation were removed.
- laser cutting was used, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 ⁇ m;
- the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste;
- the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm;
- Plasma chemical vapor deposition the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 ⁇ m.
- the exposed microcrystalline surface of the prepared diamond was (111), and the exposed microcrystalline size was micron level; the structure was columnar crystals, and the carbon content of the sp 3 structure in the diamond was 85% (testing method was XPS), SEM image is shown in FIG. 5 , the measured internal stress was 120 MPa (the test method was Raman spectroscopy), and the hardness was 95 GPa.
- This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2 mm), and comprises the following steps in sequence.
- the processing of the substrate holder was carried out according to Way I of the present disclosure, and comprised the following steps in sequence:
- the coupling mode of the plurality of energy sources was the aforementioned Mode B, that is, the coupling of arc torch, electron cyclotron resonance and magnetic resonance.
- the mouth of the arc torch was controlled at 15 mm through the coupling of the three energy sources, the temperature gradient from the torch core to the torch edge was about 40 degrees Celsius/mm, the ion energy in the diamond deposition growth area was balanced, and the plasma density was 10 ⁇ 10 10 per cm 3 .
- the deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- the temperature of the substrate holder was controlled to 1200° C., the deposition pressure was controlled to 5 kPa, and the diamond deposition speed was controlled to 20 ⁇ m/h;
- the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process
- the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system
- the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C.
- the deposition voltage deviation was not higher than 0.5 V
- the deposition current deviation was not higher than 0.5 A
- the deposition power deviation was not higher than 10 W
- the deposition gas pressure deviation was not higher than 50 PA
- the deposition gas flow deviation was not higher than 0.5 sccm
- the post-processing comprised the following steps in sequence:
- Plasma etching the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 mm, and the etching depth was 0.5 un; silicon and the nucleation were removed.
- the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 ⁇ m;
- the gyration accuracy of the spindle was less than 50 in, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- Plasma chemical vapor deposition the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 pn.
- the exposed microcrystalline surface of the prepared diamond was amorphous, and the exposed microcrystalline size was nano level; the structure was equiaxial crystal, and the carbon content of the sp 3 structure in the diamond was 80% (testing method was XPS), SEM image of the diamond is shown in FIG. 6 , the measured internal stress was 90 MPa, and the hardness was 80 GPa.
- This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2.0 mm), and comprises the following steps in sequence.
- the processing of the substrate holder was carried out according to Way II of the present disclosure, and comprised the following steps in sequence:
- the coupling mode of the plurality of energy sources was the aforementioned Mode C.
- the growth range of diamond was extended from 3-5 mm the hot filament to 5-100 mm from the hot filament, and the plasma density was 3-10 10 per cm 3 ; the ion energy in the diamond deposition growth area was balanced.
- the deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- the temperature of the substrate holder was controlled to 800° C., the deposition pressure was controlled to 4 kPa, and the diamond deposition speed was controlled to 4 ⁇ m/h;
- the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process
- the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system
- the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C.
- the deposition voltage deviation was not higher than 0.5 V
- the deposition current deviation was not higher than 0.5 A
- the deposition power deviation was not higher than 10 W
- the deposition gas pressure deviation was not higher than 50 PA
- the deposition gas flow deviation was not higher than 0.5 sccm
- the post-processing comprised the following steps in sequence:
- Plasma etching the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 ⁇ m; silicon and the nucleation were removed.
- the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 ⁇ m:
- the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- Plasma chemical vapor deposition the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 ⁇ m.
- the exposed microcrystalline surface of the prepared diamond was (100), and the exposed microcrystalline size was micron level; the structure was columnar crystal, and the carbon content of the sp 3 structure in the diamond was 80% (testing method was XPS), SEM image of the diamond is shown in FIG. 7 , the measured internal stress was 50 MPa, and the hardness was 90 GPa.
- This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 1.5 mm), and comprises the following steps in sequence.
- the processing of the substrate holder was carried out according to Way III of the present disclosure, and comprised the following steps in sequence:
- a loose layer (with a thickness of 5 ⁇ m) was formed on the surface of the titanium substrate, and the process was: depositing the loose carbon film on the titanium surface by vapor deposition, and in the deposition process, the power was 5 kW, the deposition time was 20 min, and the gas was high-purity methane:
- the coupling mode of the plurality of energy sources used in this embodiment was the aforementioned Mode D.
- the growth range of diamond was extended from 3-5 mm from the hot filament to 5-100 mm from the hot filament, and the plasma density was 3-10 10 per cm 3 ;
- the deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69;
- the etching gas was hydrogen gas (with a purity not less than 99.9999%)
- the diamond carbon source gas was methane (with a purity not less than 99.9999%)
- the assisted deposition or doping gas was argon (with a purity not less than 99.9999%):
- the temperature of the substrate holder was controlled to 800° C., the deposition pressure was controlled to 4 kPa, and the diamond deposition speed was controlled to 4 ⁇ m/h;
- the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process
- the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system
- the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C.
- the deposition voltage deviation was not higher than 0.5 V
- the deposition current deviation was not higher than 0.5 A
- the deposition power deviation was not higher than 10 W
- the deposition gas pressure deviation was not higher than 50 PA
- the deposition gas flow deviation was not higher than 0.5 sccm
- the post-processing comprised the following steps in sequence:
- Plasma etching the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 ⁇ m; silicon and the nucleation were removed.
- the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 k W, the repetition rate was 60%, and the surface roughness after cutting was 3 ⁇ m;
- the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- Plasma chemical vapor deposition the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 ⁇ m.
- the exposed microcrystalline surface of the prepared diamond was twin crystal (111), and the exposed microcrystalline size was micron level; the structure was columnar crystal, and the carbon content of the sp 3 structure in the diamond was 80% (testing method was XPS). SEM image of the diamond is shown in FIG. 8 , the measured internal stress was 150 MPa, and the hardness was 95 GPa.
- Embodiment 2 It is basically the same as Embodiment 1, differing only in that the titanium substrate was directly used as a substrate holder after being polished. The diamond thick film cannot be separated from the substrate, and the preparation of the self-supporting thick film failed.
- Embodiment 1 It is basically the same as Embodiment 1, differing only in that, in Step (2), when preparing the diamond film, only the coupling of arc torch and magnetic resonance was used.
- the prepared diamond film had poor surface uniformity, being thick in the middle while thin in the edges, and large internal stress. Two situations are prone to occur. First, the temperature gradient was too large, the thermal stress was large, and the diamond thick film was broken. 2. In the post-processing process, the diamond thick film was cracked and broken during cutting and processing.
- the diamond was of poor quality and contained high sp2 structure, and the growth rate of diamond was slow, and under the same conditions, the thickness of the preparation was 0.9 mm and the growth rate was about 1 ⁇ m/h.
- the fracture toughness of the nucleation surface of diamond was very different from that of the growth surface, and the fracture toughness of the growth surface was about 800 MPa, and the fracture toughness of the nucleation surface was 1.1 GPa.
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Abstract
Description
- The present disclosure relates to the field of preparation of superhard materials, and specifically relates to a high-quality diamond and a preparation method and application thereof.
- Diamonds have many excellent properties, such as the highest hardness, the best wear resistance, etc., which makes diamonds have a wide range of uses in many aspects. At present, the main preparation methods include high-temperature and high-pressure method, explosion method, chemical vapor deposition method and so on. The explosion method can only produce powder, while the conditions for the high-temperature and high-pressure method are relatively harsh, and the purity of the prepared diamond is low. With the development of technology, the application of plasma chemical vapor deposition method is becoming widerly, and can be used to prepare diamond coating tools, crystal diamond, free standing optical window, etc., and the main industrial methods include hot filament, microwave, arc torch, magnetron sputtering, etc. With the progress went on, people have found some usage problems, such as the hot filament method is low cost, but the quality of the diamond is not high, while the microwave method is of high quality, but the equipment is complicated, and it is difficult to scale up production and costs; the arc torch method can produce high-quality single crystal optical-grade diamond, but the internal stress of the diamond is relatively high, the cost is relatively high, and the product is less than 80%. People have adopted various methods, such as temperature field simulation, flow field simulation, plasma emission spectrum test, stress field simulation & test, etc. People have approached the limitation with a single method, but the result is still not very well.
- Shanghai Zhang Zhiming groups introduced bias voltage hot filament plasma technology, which greatly enlarged the deposition parameters, and approach a great application on wire drawing dies area. Beijing and Shijiazhuang Lv Fanxiu groups introduced the magnetic to the arc torch, which lead to greatly improvement on temperature gradient of the torch, thereby reducing the stress of prepared diamond thick films, and improving the yield. However, the above-mentioned methods are still difficult to apply chemical vapor deposition diamond technology on industrial application, and the uniformity, toughness, internal stress, service life, diamond quality, etc. of the prepared diamond still need to be improved.
- The present disclosure is intended to overcome the deficiencies of the prior art, and to provide an improved preparation method for diamond, which can stably obtain high-quality diamonds.
- The present disclosure further provides a diamond prepared according to the above-mentioned method at the same time.
- The present disclosure further provides use of the diamond prepared above-mentioned in the preparation of cutting tools and heat sinks at the same time.
- To achieve the above purposes, a technical solution employed the present disclosure is:
- a method for preparing diamond, comprises the following steps in sequence:
- (1) processing a substrate material of a substrate holder to obtain a surface that is easily separated from diamond films, wherein the substrate material of the substrate holder is processed in any of the following ways:
- Way I: using a first material as the substrate material, performing surface polished processing, and forming a first nucleation layer on a surface of the substrate material to obtain the substrate holder, the first material being a material that does not react with carbon at the vapor deposition temperature of diamond, and the material of the first nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- Way II: using a second material as the substrate material, performing surface polished processing, and forming a second nucleation layer to obtain the substrate holder, the second material being a material that softens or melts at the vapor deposition temperature of diamond, and the material of the second nucleation layer is selected from carbon, silicon, silicon carbide, silicon nitride, and combinations thereof;
- Way III: processing the surface of the substrate material and forming a loose layer and a third nucleation layer thereon in sequence to serve as the substrate holder, a material of the loose layer is selected from amorphous carbon, amorphous silicon, diamond micro-powder, silica micro-powder, aluminum oxide micro-powder, and combinations thereof; a material of the third nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- (2) using a plasma chemical vapor deposition method to form a diamond film layer on the surface of the substrate holder, wherein the plasma chemical vapor deposition method uses a multi-energy sources to couple with plasma, and the plurality of energy sources are 2, 3, or more kinds;
- (3) post-processing the diamond film layer to remove impurity material on the diamond surface and a nucleation layer and/or stress layer with inconsistent properties of a main body of the diamond film.
- Further, in Way I, the first material may be specifically selected from materials that do not react with carbon, such as copper, copper alloy, silicon carbide, aluminum oxide, silicon dioxide, and microcrystalline glass ceramics.
- In Way II, the second material may be selected from mercury, plumbum, tin, aluminum, sodium, and alloys thereof, etc.
- In Way III, the substrate material is not particularly limited, and may be any suitable material, specifically, it may be selected from those materials that react with diamond at the vapor deposition temperature of diamond, or may be selected from the first material and the second material mentioned above.
- As a preferred implementation of the present disclosure, in Way III, the substrate material is selected from those materials that react with diamond at the vapor deposition temperature of diamond, specifically, for example, iron, iron alloy, nickel, nickel alloy, titanium, tungsten, molybdenum and alloys thereof, etc.
- Further, in Way I, the first nucleation layer may have a thickness of 5 nm-5 μm, and the existence of the first nucleation layer is very helpful for the growth of diamond in the subsequent steps and greatly improves its growth efficiency. The nucleation density of the first nucleation layer is not particularly limited, but from an industrial point of view, it is preferably not lower than 1.0×1013 per cm2. The thickness of the first nucleation layer may more preferably be 50 nm-500 nm.
- Further, in Way II, the second nucleation layer has a thickness of 200 nm-5 μm, and the provision of the second nucleation layer can effectively ensure the overall structure and integrity of the finally formed and separated diamond film. The nucleation density of the second nucleation layer is also not particularly limited, but from an industrial point of view, it is preferably not lower than 1.0×1013 per cm2. The thickness of the second nucleation layer may more preferably be 500 nm-5 μm, and even more preferably be 1-5 μm.
- Further, in Way III, the loose layer has a thickness of 0.01 nm-1000 μm, and the function of the loose layer is to facilitate the separation of the formed diamond film from the substrate holder and at the same time facilitate the diamond nucleation, in terms of its function, there is no special requirement for its specific thickness if it is suitable for practical industrial production. The substrate holder adopting Way III is particularly suitable for obtaining a self-supporting diamond thick film with perfect crystal form. The material of the loose layer is not limited to those mentioned above, and may also be other materials having a crystal structure similar to that of diamond.
- Further, the loose layer may be a loose layer in the initial stage, or it may be formed by vaporized and decomposed during the diamond deposition process.
- Further, in Way III, the third nucleation layer has the same function as the first nucleation layer, which is to promote the deposition and growth of diamond, and its thickness may be 0.1 nm-100 μm, and the nucleation density is not lower than 1×1013 per cm2.
- Further, the loose layer can be prepared using processes known in the art such as chemical vapor deposition, thermal deposition, spin coating, or Czochralski method. The first nucleation layer, the second nucleation layer, and the third nucleation layer may be respectively formed using a chemical vapor deposition method.
- Further, in Step (1), the surface of the substrate holder is a nano-level plane, a micron-level plane or a millimeter-level plane. Specifically, the surface finish of the nano-level plane is 0.1-1000 nm, the surface finish of the micron-level plane is 0.1-1000 μm, and the surface finish of the millimeter-level plane is 0.1-1000 mm. Further preferably, the surface finish of the nano-level plane is 0.1-500 nm, the surface finish of the micron-level plane is 10-800 μm, and the surface finish of the millimeter-level plane is 1-1000 mm. Still further preferably, the surface finish of the nano-level plane is 1-500 nm, the surface finish of the micron-level plane is 50-800 μm, and the surface finish of the millimeter-level plane is 100-1000 mm. Wherein, as a preference, the surface of the substrate holder is a nano-level plane.
- Further, in Step (2), in the plasma chemical vapor deposition method, the temperature of the substrate holder is preferably from room temperature to 1200° C., further preferably 500-1200° C., and still further preferably 800-1000° C. The deposition pressure is generally 0.01 to 200 kPa, preferably 0.1 to 20 kPa, further preferably 1 to 10 kPa, and still further preferably 2 to kPa. The speed of depositing diamond may be controlled between 0.01-1000 μm/h, but from the perspective of ensuring the quality of diamond, preferably, the speed is controlled to 0.01-200 μm/h, and further preferably, the speed is controlled to 0.1-100 μm/h. Still further preferably, the speed is controlled to 1-50 μm/h.
- Further, in the plasma chemical vapor deposition method, the deposition gas is a mixture of an etching gas, a diamond carbon source gas, an assisted deposition or doping gas.
- Further preferably, in Step (2), the etching gas is selected from hydrogen, ammonia, fluorine, hydrogen fluoride, hydrogen chloride, and combinations thereof, and the diamond carbon source gas is selected from methane, acetone, acetylene, and combinations thereof.
- Further preferably, in Step (2), the assisted deposition or doping gas is selected from nitrogen, argon, xenon, borane, silane, phosphorane, and combinations thereof.
- Further preferably, a purity of each gas in the deposition gas is not less than 99.9999%.
- According to a preferred aspect of the present disclosure, in Step (2), the energy sources are selected from magnetic resonance, electric arc, hot filament, flame, microwave, radio frequency, high frequency, direct current, laser, ion beam, electron beam, electron cyclotron resonance, and also meet the following (i) or (ii):
- (i) the plurality of energy sources comprises at least magnetic resonance, and the energy of the plasma in the diamond deposition area is equalized through a coupling of the plurality of energy sources;
- (ii) the plurality of energy sources does not comprise magnetic resonance, when performing the plasma chemical vapor deposition, magnetic confinement is applied to shield more than 99.9% of energy ions above 5 keV from the diamond deposition area;
- Through the coupling of the plurality of energy sources, the plasma density in the diamond deposition area is controlled to be (0.1-100)×1010 per cm3.
- Further, the electric arc may be a cathode arc or an arc torch.
- Further and preferably, the coupling of the plurality of energy sources adopts one of the following coupling modes:
- Mode A: the coupling of the plurality of energy sources is the coupling of laser and/or microwave, cathode arc, electron cyclotron resonance;
- Mode B: the coupling of the plurality of energy sources is the coupling of arc torch, magnetic resonance and electron cyclotron resonance;
- Mode C: the coupling of the plurality of energy sources is the coupling of magnetic resonance, hot filament and direct current;
- Mode D: the coupling of the plurality of energy sources is the coupling of magnetic resonance, hot filament and high frequency;
- wherein, at the time Mode A is adopted, a magnetic confinement is applied.
- According to a specific and preferred aspect of the present disclosure, in Mode A, the laser and/or microwave are first coupled with the cathode arc to smoothly initiate the cathode arc sustainably and stably generate the cathode arc, and after the generated plasma excited by the cathode arc passes through the magnetic confinement to shield high-energy ions (ions with energy higher than 5 keV), it couples with the electron cyclotron resonance plasma.
- According to another specific and preferred aspect of the present disclosure, in Mode B, the plasma generated by the arc torch is first coupled with the magnetic resonance plasma, and through the coupling, at a position of 10-15 mm from the arc torch mouth, a temperature gradient from a torch core to a torch edge is 40 to 50 degrees Celsius/mm. The internal thermal stress of the formed diamond film layer is less than 200 MPa. Compared with using a single arc torch (the temperature gradient from the torch core to the torch edge is 400-500 degrees Celsius/mm, the thermal stress inside the prepared diamond is above 1 G, and the growth area of the diamond is only a tube conical area of 3-5 mm from the arc edge), the effect of coupling is very significant.
- According to still another specific and preferred aspect of the present disclosure, in Mode C, the diamond deposition rate may reach 40-50 μm/h through coupling, and the hardness of the obtained diamond film reaches 80-100 GPa.
- Preferably, the plasma density in the diamond deposition area is 0.1×1010-10×1010 per cm3, and further preferably, the plasma density in the diamond deposition area is 0.1×1010-1×1010 per cm3.
- According to yet another particularly preferred and specific aspect of the present disclosure, in Mode C, through coupling, a diamond deposition area with a distance of 5-100 mm from the hot filament is obtained (while only the hot filament is used as an energy source, the effective diamond deposition area is a tubular area of 3-5 mm from the hot filament).
- According to still another particularly preferred and specific aspect of the present disclosure, in Mode D, when the diamond deposition rate reaches 40-50 μm/h through coupling, the hardness of the obtained diamond film reaches 80-100 GPa. With a single energy source or a simple superposition of a plurality of energy sources, the hardness of the obtained diamond can only reach 30-70 GPa when the deposition rate is 2-5 μm/h. If the deposition rate is further increased, the hardness of the diamond will further decrease.
- Preferably, in Step (2), the environment or conditions of chemical vapor deposition are balance controlled, and the environment or conditions are one or more of deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow rate. The specific control method can be conventional means known in the art. Further, when a photoelectric self-feedback control system is used to perform the balance control, the photoelectric self-feedback control system comprises a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation is not higher than 0.5° C., the deposition voltage deviation is not higher than 0.5 V the deposition current deviation is not higher than 0.5 A, the deposition power deviation is not higher than 10 W, the deposition gas pressure deviation is not higher than 50 Pa, and the deposition gas flow deviation is not higher than 0.5 sccm.
- Further, by using high thermal conductivity copper and the like for the preparation of the substrate holder, the temperature difference range of the substrate holder is controlled to be less than 0.5° C., and materials with different thermal conduction rates are padded between the substrate holder and a heat dissipation water-cooling cavity, such as graphite, copper, stainless steel, and foamed alumina, to control the thermal conduction rate, the temperature gradient of the base of the substrate holder, and the cooling rate, to improve the quality of diamond deposition, and to reduce the temperature difference stress of diamond.
- In Step (2), it is also preferable to control the temperature gradient and the energy transfer direction of the temperature field in the diamond deposition area to control the deposition of diamond, as desired.
- In a specific and preferred manner according to the present disclosure, in Step (3), the post-processing preferably comprises chemical processing, plasma etching, cutting, grinding and polishing carried out in sequence.
- In another embodiment according to the present disclosure, in Step (3), the post-processing comprises cutting and grinding and polishing carried out in sequence.
- Further, in Step (3), the chemical processing is processing with an organic acid and/or an inorganic acid, or a combination thereof with hydrogen peroxide;
- In Step (3), the cutting is laser cutting, the laser has a wavelength of 100-1100 nm, a laser power of 0.1-100 kW, and a repetition rate of 0.1-99.9%, and the surface roughness after cutting is 0.1 nm-100 μm; wherein, the laser cutting is pulsed laser cutting, when used for cutting diamond, by controlling the overlap rate between the spots generated by two adjacent pulsed lasers, and combined with the control of the laser spot diameter, it can be realized that the diamond after processed can achieve the desired ideal surface finish, therefore, the aforementioned “repetition rate of 0.1-99.9%” means that the overlap rate between the spots generated by two adjacent pulsed lasers is 0.1-99.9%.
- In Step (3), the grinding and polishing is mechanical grinding. Further, a gyration accuracy of the grinding spindle is less than 50 nm, the vibration amplitude of the grinding disc is less than 50 nm, and the grinding paste is diamond grinding paste; the grinding disc is a phosphorous cast iron grinding disc with a rotation speed of 0.1-300,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer is not less than 50 nm;
- In Step (3), in the plasma etching, the etching gas is composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:0.1-100:0.1-100; the energy source is direct current glow plasma, the etching gas pressure is 0.1-100 kPa, the etching time is 30 s-120 min, and the etching depth is 50-100 nm.
- According to some preferred aspects of the present disclosure, the preparation method further comprises a repair step performed after Step (3), and the repair step is plasma chemical vapor deposition and/or plasma etching, and in the plasma chemical vapor deposition, the deposition gas is composed of methane, hydrogen and argon with a volume ratio of 1:(0.1-200):(0.1-100); the deposition pressure is 0.1-100 kPa, the deposition time is 1 min-120 min, and the deposition thickness is 0.1-100 nm.
- According to some specific aspects of the present disclosure, the obtained diamond has the following characteristics:
- The exposed microscopic surface is selected from (111) crystal faces, (100) crystal faces, (110) crystal faces, amorphous crystal faces, and combinations thereof, and the size of the exposed microscopic crystal form is nano level (may be 0.1-1000 nm), micron level (may be 0.1-1000 μm) or millimeter level (may be 0.1-1000 mm);
- Its structure is single crystal, nanocrystal, microcrystal, columnar crystal, or a combination of various crystal indefinite laminates, the thickness of the laminates is 0.1 nm-1000 μm, and the number of laminated layers is two, three or more, and the number of layers is not limited:
- The carbon content of its sp3 structure is 80-100%.
- Another technical solution provided by the present disclosure is, a diamond prepared according to the above-mentioned method. The diamond has good toughness, impact resistance and long service life.
- Another technical solution provided by the present disclosure is, use of the diamond above-mentioned in the preparation of cutting tools and heat sinks.
- Due to the use of the above technical solutions, the present disclosure has the following advantages over the prior art:
- The preparation method proposed by the present disclosure comprehensively designs the whole process, especially by processing of the substrate material of the substrate holder in the early stage, the coupling of the plurality of energy sources in the deposition process, and specific post-processing, the preparation of a stable and uniform diamond film is achieved. The diamond film obtained by the method of the present disclosure, especially the diamond thick film, has good toughness, impact resistance and long service life. The method of the present disclosure has low cost, high production efficiency and good stability, and is suitable for large-scale diamond production of high-quality large-area diamond films.
-
FIGS. 1 to 4 show the designs of the respective energy sources in a plurality of energy source coupling Modes A, B, C, and D in sequence: -
FIG. 5 is an SEM image of the diamond made in Embodiment 1 of the present disclosure: -
FIG. 6 is an SEM image of the diamond made in Embodiment 2 of the present disclosure; -
FIG. 7 is an SEM image of the diamond made in Embodiment 3 of the present disclosure; -
FIG. 8 is an SEM image of the diamond made in Embodiment 4 of the present disclosure; - In
FIG. 1, 11 —arc cathode; 12—arc anode; 13—microwave feed inlet; 14—laser feed inlet; 15—magnetic mirror coil; 16—first electron cyclotron coil; 17—first deposition area; 18—first deposition chamber; - In
FIG. 2, 21 —arc torch inlet; 22—equalizing magnetic field coil; 23—second electron cyclotron coil; 24—second deposition area; 25—second deposition chamber; - In
FIG. 3, 31 —pulse electrode; 32—first hot filament; 33—first coupling coil; 34—deposition substrate holder; 35—third deposition chamber; - In
FIG. 4, 41 —second coupling coil; 42—second hot filament; 43—high frequency; 44—upper deposition substrate holder; 45—lower deposition substrate holder; 46—fourth deposition chamber. - Compared with the existing preparation method of chemical vapor deposition diamond film, especially thick film, the improvement mainly lies in:
- on the one hand, the fine processing of the substrate holder facilitates the stripping of the diamond, reduces the stress of the diamond, and obtains high-quality diamonds.
- Specifically, there are three schemes for processing the substrate material of the substrate holder:
- Way I: using a first material as the substrate material, performing surface polished processing, and forming a first nucleation layer on a surface of the substrate material to obtain the substrate holder, the first material being a material that does not react with carbon at the vapor deposition temperature of diamond, and the material of the first nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof;
- Way II: using a second material as a substrate material, performing surface polished processing, and forming a second nucleation layer to obtain the substrate holder, the second material being a material that softens or melts at the vapor deposition temperature of diamond, and the material of the second nucleation layer is selected from carbon, silicon, silicon carbide, silicon nitride, and combinations thereof;
- Way III: processing the surface of the substrate material and forming a loose layer and a third nucleation layer thereon in sequence to serve as a substrate holder, the material of the loose layer is selected from the group consisting of amorphous carbon, amorphous silicon, diamond micro-powder, silica micro-powder, aluminum oxide micro-powder, and combinations thereof, the material of the third nucleation layer is selected from diamond, amorphous carbon, silicon carbide, silicon, germanium, beryllium, and combinations thereof.
- The substrate holders processed or prepared according to the above three schemes are not only very conducive to the growth of the diamond film, but also easy to separate from the diamond film after the diamond film is formed in the later stage, ensuring that a diamond with complete and large area is obtained.
- The present disclosure further obtains plasma that is most conducive to diamond formation through the coupling of a plurality of energy sources, obtaining high-quality diamonds with higher efficiency, and reducing energy consumption while improving diamond preparation efficiency.
- Further,
- (1) high energy density coupling in the diamond growth area
- Limited by the melting point of tungsten, the power limit of the magnetron, and the temperature limit of the arc torch tip, etc., the energy density of a single hot filament, microwave, and arc torch is limited to 500 W per square millimeter or less, and through the coupling of a plurality of energy sources, the energy density can be significantly increased, for example, the use of a regular pentagonal cavity structure to design a microwave resonant cavity, can increase the energy density of microwave plasma by five times; the coupling of hot filament and electric arc process can increase the energy density by more than two times. The coupling of multiple energy sources is not a single energy superposition. Because diamond is deposited from a low-temperature non-equilibrium plasma, and the electron temperature is much higher than the ion temperature, the purpose of coupling a plurality of energy sources is to use more energy to generate effective excitation ionization, and increase the number and proportion of the deposited diamond CH2 groups (since the ionized ion energy is not the higher the better, the generation and recombination of free ions requires specific energy level transitions and frequencies and free paths, the coupling of a plurality of energy sources of the present disclosure can fit the feed-in energy with the characteristic spectrum, frequency, and free path of the plasma, to generate resonance or excitation, and promote effective excitation ionization, while the simple superposition of a plurality of energy sources is an ineffective superposition, which only generates excess light and heat, causes excess heat transfer and special requirements for materials and equipment structure, but is not beneficial to the energy density of the diamond production area). It increases the effective energy consumption at the same power by 20-30 times; that is, at the same power, the deposition speed of the same quality diamond is 20-30 times that of a single energy source.
- (2) highly uniform energy source coupling in the diamond growth area
- The hot filament is a linear energy source, the microwave is a spherical energy source, the arc torch is a point-like energy source, and the suitable areas for diamond growth are a tubular area 3-5 mm from the hot filament, and a spherical shell area 3-5 mm from the standing microwave, and a tube cone-shaped area 3-5 mm from the arc edge. A single energy source can only form a very small confined diamond deposition growth area, and through the coupling of a plurality of energy sources, a specific uniform area can be stretched, and the plasma area for effective diamond growth can be stretched by 5-100 mm:
- (3) high-energy ions that are unfavorable to diamond growth are shielded outside of the diamond growth area through coupling or the high-energy ions are controlled in the diamond growth area to be as few as possible through coupling.
- The core areas of plasmas of hot filament, microwave, and electric arc have large amounts of high-energy plasmas, especially ions with energy higher than 5 keV. These ions are useless for diamond deposition but can graphitize the diamond that has been prepared and reduce the quality of the diamond. Through coupling with magnetic resonance, the plasma energy can be balanced to the greatest extent and high-energy ions can be effectively reduced; by applying magnetic confinement, more than 99.9%, further, more than 99.99%, and still further, more than 99.999% of high-energy ions (50 keV) are shielded from the diamond deposition area.
- See
FIG. 1 , a way of coupling a plurality of energy sources (Mode A) is showed. Various energy sources comprise cathode arc, electron cyclotron resonance, and optional microwaves and lasers. A voltage is applied between anarc cathode 11 and anarc anode 12, and the voltage is not enough to be in a discharge state, and microwave and laser are fed through amicrowave inlet 13 and alaser inlet 14 respectively, or only one of them is fed, through their excitation, the plasma arc ignition is generated, so that a smooth discharge is generated between thearc anode 12 and thearc cathode 11 and the discharge continues steadily. Using laser or microwave or both for excitation can avoid a large number of large particle ions flying out at the moment of high voltage discharge. The cathode is a high-purity carbon target. The generated plasma removes large particles and high-energy ions through the magnetic confinement effect of amagnetic mirror coil 15, and at the same time, under the condition of the electron cyclotron magnetic field formed by a firstelectron cyclotron coil 16, only hydrogen ions and carbon ions suitable for diamond growth reach afirst deposition area 17 of afirst deposition chamber 18, thereby obtaining high-quality diamonds. - See
FIG. 2 , another way of coupling a plurality of energy sources (Mode B) is showed. The employed plurality of energy sources comprises arc torch, magnetic resonance and electron cyclotron resonance. After the arc torch is ejected from the arc torch mouth, it enters the cavity from anarc torch inlet 21 and uses an equalizingmagnetic field coil 22 to apply a primary magnetic resonance (equalizing magnetic field) to force the center temperature and high-energy ions of the arc torch to deflect and collide with the ions on the edge of the arc torch to generate exchange. The temperature gradient is reduced from 2000-4000 degrees Celsius/mm at the arc torch outlet to 400-500 degrees Celsius/mm, and further homogenizes under the condition of the electron cyclotron magnetic field formed by a secondelectron cyclotron coil 23 to charge the central ion by collision, and through the control of distance and magnetic field, the temperature gradient at the position of 10-15 mm from the mouth of the arc torch is further reduced from 400-500 degrees Celsius/mm to 40-50 degrees Celsius/mm, and at the same time, high-energy particles greater than 5 keV are deflected by a magnetic field and collide and couple to reduce to less than 5 keV. Through the coupling design, without changing the overall energy density of the plasma, the energy of the plasma in asecond deposition area 24 in asecond deposition chamber 25 is equalized, and by controlling the frequency and size of the precisely coupled magnetic field, the proportion of ions producing diamond is oriented to increase. - See
FIG. 3 , still a way of coupling a plurality of energy sources (Mode C) is showed. The employed plurality of energy sources is magnetic resonance (specifically, magnetic cyclotron resonance), hot filament and direct current. Apulse electrode 31, that is, a pulsed direct current bias power source, is applied between a firsthot filament 32 and adeposition substrate holder 34, and a first coupling coil 33 is used to apply a magnetic cyclotron resonance magnetic field around thedeposition substrate holder 34. By controlling the size and changing direction of the magnetic field, the density and uniformity of plasma on the surface of thedeposition substrate holder 34 in athird deposition chamber 35 are increased. - See
FIG. 4 , yet a way of coupling a plurality of energy sources (Mode D) is showed. The employed plurality of energy sources is magnetic resonance (specifically, magnetic cyclotron resonance), hot filament and high frequency. An upperdeposition substrate holder 44 and a lower deposition substrate table 45 are respectively arranged on two parallel sides of a secondhot wire 42 to produce diamonds.High frequency 43 is used to generate a high frequency discharge between the two substrate holders. A magnetic cyclotron resonance magnetic field is applied around the lowerdeposition substrate holder 45 using asecond coupling coil 41. By controlling the size and changing direction of the magnetic field, the density and uniformity of plasma on the surface of the substrate holder are increased. - Through the post-processing process of the diamond free-standing thick film, the present disclosure further improves the toughness and impact resistance of the diamond and improves the service life of the diamond.
- On the basis of the above process improvement, it can also be combined with the relatively mature intelligent control technology, and the multi-mode closed-loop control technology may be used in the vapor deposition process of diamond, to realize the balance control of the key environment, conditions and temperature field of the deposition, reduce manual operation error, and improve the quality and stability of production.
- The method of the present disclosure is also applicable to the production processes of plasma chemical vapor deposition thin film coated cutting tools, single crystal diamond, polycrystalline optical-grade diamond, etc., and can also be expected to obtain the desired effect.
- The high-quality diamond self-supporting thick film prepared by the method of the present disclosure is expected to greatly reduce the preparation cost of diamond thick film cutting tools, and improve processing quality, and it can also be applied to the field of heat sinks.
- In the following, the specific embodiments are combined to further explain the above solutions in detail; it should be understood that, those embodiments are to explain the basic principle, major features and advantages of the present disclosure, and the present disclosure is not limited by the scope of the following embodiments; the implementation conditions employed by the embodiments may be further adjusted according to particular requirements, and undefined implementation conditions usually are conditions in conventional experiments. If no special instructions are given in the following embodiments, all raw materials are commercially available or prepared by conventional methods in the field.
- This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2 mm), and comprises the following steps in sequence.
- (1) Processing of the Substrate Holder
- The processing of the substrate holder was carried out according to Way III of the present disclosure, and comprised the following steps in sequence:
- (i) a titanium substrate (with a thickness of 6 mm) was taken and polished to obtain a nano-level surface (with surface finish <5 nm):
- (ii) a loose layer (with a thickness of 5 μm) was formed on the surface of the titanium substrate, and the process was: depositing the loose carbon film on the titanium surface by vapor deposition, and in the deposition process, the power was 5 kW, the deposition time was 20 min, and the gas was high-purity methane:
- (i) magnetron sputtering was used to form a nucleation layer (with a thickness of 200 nm, and a nucleation density about 1.5×1013 per cm2) on the aforementioned loose layer, and the specific conditions and process were: pulsed direct current magnetron sputtering, the sputtering power was 300 W, the target material was high-purity silicon, the sputtering time was 5 min, the nucleation process gas volume ratio was methane:hydrogen=5:100, the nucleation time was 20 min, and the nucleation pressure was 6 kPa.
- (2) Preparation of Diamond Film by Multi-Energy Sources Coupled Plasma Chemical Vapor Deposition
- In this embodiment, the diamond film layer was the coupling of five energy sources, namely electric arc, electron cyclotron resonance, magnetic resonance, laser and microwave, and the specific coupling mode was the aforementioned Mode A, the plasma density in the diamond deposition growth area was controlled to be 1×1010 per cm3;
- The deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- The temperature of the substrate holder was controlled to 900° C., the deposition pressure was controlled to 5 kPa, and the diamond deposition speed was controlled to 8 μm/h.
- In this step, the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process, the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C., the deposition voltage deviation was not higher than 0.5 V, the deposition current deviation was not higher than 0.5 A, the deposition power deviation was not higher than 10 W, the deposition gas pressure deviation was not higher than 50 Pa, and the deposition gas flow deviation was not higher than 0.5 sccm;
- (3) Post-Processing
- The post-processing comprised the following steps in sequence:
- Chemical treatment: sulfuric acid (96%) and hydrogen peroxide (30%) were used for etching; the etching time was 10 min, the temperature was 160 degrees, and graphite and substrate residues were removed;
- Plasma etching: the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 μm; silicon and the nucleation were removed.
- Cutting: laser cutting was used, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 μm;
- Grinding and polishing: mechanical grinding, the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm;
- (4) Repair
- Plasma chemical vapor deposition: the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 μm.
- The exposed microcrystalline surface of the prepared diamond was (111), and the exposed microcrystalline size was micron level; the structure was columnar crystals, and the carbon content of the sp3 structure in the diamond was 85% (testing method was XPS), SEM image is shown in
FIG. 5 , the measured internal stress was 120 MPa (the test method was Raman spectroscopy), and the hardness was 95 GPa. - This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2 mm), and comprises the following steps in sequence.
- (1) Processing of the Substrate Holder
- The processing of the substrate holder was carried out according to Way I of the present disclosure, and comprised the following steps in sequence:
- (i) a high-purity copper (with a thickness of 6 mm) was taken and polished to obtain a nano-level surface (with surface finish <5 nm):
- (ii) magnetron sputtering was used to form a nucleation layer (with a thickness of 200 nm, and a nucleation density about 1.5×1013 per cm2) on the copper surface, and the specific conditions and process were: pulsed direct current magnetron sputtering, the sputtering power was 300 W, the target material was high-purity silicon, the sputtering time was 5 min, the nucleation process gas volume ratio was methane:hydrogen=5:100, the nucleation time was 20 min, and the nucleation pressure was 6 kPa.
- (2) Preparation of Diamond Film by Multi-Energy Sources Coupled Plasma Chemical Vapor Deposition
- In this embodiment, the coupling mode of the plurality of energy sources was the aforementioned Mode B, that is, the coupling of arc torch, electron cyclotron resonance and magnetic resonance. The mouth of the arc torch was controlled at 15 mm through the coupling of the three energy sources, the temperature gradient from the torch core to the torch edge was about 40 degrees Celsius/mm, the ion energy in the diamond deposition growth area was balanced, and the plasma density was 10×1010 per cm3.
- The deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- The temperature of the substrate holder was controlled to 1200° C., the deposition pressure was controlled to 5 kPa, and the diamond deposition speed was controlled to 20 μm/h;
- In this step, the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process, the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C., the deposition voltage deviation was not higher than 0.5 V, the deposition current deviation was not higher than 0.5 A, the deposition power deviation was not higher than 10 W, the deposition gas pressure deviation was not higher than 50 PA, and the deposition gas flow deviation was not higher than 0.5 sccm;
- (3) Post-Processing
- The post-processing comprised the following steps in sequence:
- Chemical treatment: sulfuric acid (96%) and hydrogen peroxide (30%) were mixed at a mass ratio of 1:1 and then used for etching; the etching time was 10 min, the temperature was 160 degrees, and graphite and substrate residues were removed;
- Plasma etching: the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 mm, and the etching depth was 0.5 un; silicon and the nucleation were removed.
- Cutting: the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 μm;
- Grinding and polishing: mechanical grinding, the gyration accuracy of the spindle was less than 50 in, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- (4) Repair
- Plasma chemical vapor deposition: the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 pn.
- The exposed microcrystalline surface of the prepared diamond was amorphous, and the exposed microcrystalline size was nano level; the structure was equiaxial crystal, and the carbon content of the sp3 structure in the diamond was 80% (testing method was XPS), SEM image of the diamond is shown in
FIG. 6 , the measured internal stress was 90 MPa, and the hardness was 80 GPa. - This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 2.0 mm), and comprises the following steps in sequence.
- (1) Processing of the Substrate Holder
- The processing of the substrate holder was carried out according to Way II of the present disclosure, and comprised the following steps in sequence:
- (i) an aluminum substrate (with a thickness of 6 mm) was taken and polished to obtain a nano-level surface (with surface finish <5 nm);
- (ii) magnetron sputtering was used to form a nucleation layer (with a thickness of 5 nm, and a nucleation density about 1.5×1013 per cm2) on the aluminum substrate surface, and the specific conditions and process were: pulsed direct current magnetron sputtering, the sputtering power was 400 W, the target material was high-purity silicon, the sputtering time was 25 min. the nucleation process gas volume ratio was methane:hydrogen=5:100, the nucleation time was 20 min, and the nucleation pressure was 6 kPa.
- (2) Preparation of Diamond Film by Multi-Energy Sources Coupled Plasma Chemical Vapor Deposition
- In this embodiment, the coupling mode of the plurality of energy sources was the aforementioned Mode C. Through the coupling of the three energy sources, the growth range of diamond was extended from 3-5 mm the hot filament to 5-100 mm from the hot filament, and the plasma density was 3-1010 per cm3; the ion energy in the diamond deposition growth area was balanced.
- The deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%).
- The temperature of the substrate holder was controlled to 800° C., the deposition pressure was controlled to 4 kPa, and the diamond deposition speed was controlled to 4 μm/h;
- In this step, the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process, the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C., the deposition voltage deviation was not higher than 0.5 V, the deposition current deviation was not higher than 0.5 A, the deposition power deviation was not higher than 10 W, the deposition gas pressure deviation was not higher than 50 PA, and the deposition gas flow deviation was not higher than 0.5 sccm;
- (3) Post-Processing
- The post-processing comprised the following steps in sequence:
- Chemical treatment: sulfuric acid (96%) and hydrogen peroxide (30%) were mixed at a mass ratio of 1:1 and then used for etching; the etching time was 10 min, the temperature was 160 degrees, and graphite and substrate residues were removed;
- Plasma etching: the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 μm; silicon and the nucleation were removed.
- Cutting: the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 kW, the repetition rate was 60%, and the surface roughness after cutting was 3 μm:
- Grinding and polishing: mechanical grinding, the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- (4) Repair
- Plasma chemical vapor deposition: the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 μm.
- The exposed microcrystalline surface of the prepared diamond was (100), and the exposed microcrystalline size was micron level; the structure was columnar crystal, and the carbon content of the sp3 structure in the diamond was 80% (testing method was XPS), SEM image of the diamond is shown in
FIG. 7 , the measured internal stress was 50 MPa, and the hardness was 90 GPa. - This embodiment provides a method for preparing diamond, which can prepare a self-supporting diamond thick film (with a thickness of 1.5 mm), and comprises the following steps in sequence.
- (1) Processing of the Substrate Holder
- The processing of the substrate holder was carried out according to Way III of the present disclosure, and comprised the following steps in sequence:
- (i) a titanium substrate (with a thickness of 6 mm) was taken and polished to obtain a nano-level surface (with surface finish <5 nm);
- (ii) a loose layer (with a thickness of 5 μm) was formed on the surface of the titanium substrate, and the process was: depositing the loose carbon film on the titanium surface by vapor deposition, and in the deposition process, the power was 5 kW, the deposition time was 20 min, and the gas was high-purity methane:
- (iii) magnetron sputtering was used to form a nucleation layer (with a thickness of 200 nm, and a nucleation density about 1.5×1013 per cm2) on the aforementioned loose layer, and the specific conditions and process were: pulsed direct current magnetron sputtering, the sputtering power was 300 W, the target material was high-purity silicon, the sputtering time was 5 min, the nucleation process gas volume ratio was methane:hydrogen=5:100, the nucleation time was 20 min, and the nucleation pressure was 6 kPa.
- (2) Preparation of Diamond Film by Multi-Energy Sources Coupled Plasma Chemical Vapor Deposition
- The coupling mode of the plurality of energy sources used in this embodiment, was the aforementioned Mode D. Through the coupling of the three energy sources, the growth range of diamond was extended from 3-5 mm from the hot filament to 5-100 mm from the hot filament, and the plasma density was 3-1010 per cm3;
- The deposition gas was a mixture of an etching gas, a diamond carbon source gas and an assisted deposition or doping gas, and a volume ratio of the etching gas, diamond carbon source gas, and assisted deposition or doping gas was 1:100:69; the etching gas was hydrogen gas (with a purity not less than 99.9999%), the diamond carbon source gas was methane (with a purity not less than 99.9999%), and the assisted deposition or doping gas was argon (with a purity not less than 99.9999%):
- The temperature of the substrate holder was controlled to 800° C., the deposition pressure was controlled to 4 kPa, and the diamond deposition speed was controlled to 4 μm/h;
- In this step, the preparation method further comprised a photoelectric self-feedback control system that controls the deposition temperature, deposition voltage, deposition current, deposition power, deposition gas pressure, and deposition gas flow during the deposition process, the photoelectric self-feedback control system comprised a temperature measurement and control system, a voltage self-feedback control system, a current self-feedback control system, a power self-feedback control system, and an emission spectrum self-feedback control system, the temperature can be controlled by the cooling water flow and the temperature of the cooling water, and through the control of the photoelectric self-feedback control system, the deposition temperature deviation was not higher than 0.5° C., the deposition voltage deviation was not higher than 0.5 V, the deposition current deviation was not higher than 0.5 A, the deposition power deviation was not higher than 10 W, the deposition gas pressure deviation was not higher than 50 PA, and the deposition gas flow deviation was not higher than 0.5 sccm;
- (3) Post-Processing
- The post-processing comprised the following steps in sequence:
- Chemical treatment: sulfuric acid (96%) and hydrogen peroxide (30%) were mixed at a mass ratio of 1:1 and then used for etching; the etching time was 10 min, the temperature was 160 degrees, and graphite and substrate residues were removed:
- Plasma etching: the etching gas was composed of oxygen, hydrogen and hydrogen fluoride gas, with a volume ratio of 1:1:0.5; the energy excitation source was direct current glow plasma, the etching gas pressure was 0.2 kPa, the etching time was 20 min, and the etching depth was 0.5 μm; silicon and the nucleation were removed.
- Cutting: the cutting was laser cutting, the wavelength of the laser was 193 nm, the laser power was 2 k W, the repetition rate was 60%, and the surface roughness after cutting was 3 μm;
- Grinding and polishing: mechanical grinding, the gyration accuracy of the spindle was less than 50 nm, the vibration amplitude of the grinding disc was less than 50 nm, and the grinding paste was diamond grinding paste; the grinding disc was a phosphorous cast iron grinding disc with a rotation speed of 160,000 revolutions/s and using an air-floating spindle; the thickness of the grinding surface damage layer was not less than 50 nm.
- (4) Repair
- Plasma chemical vapor deposition: the deposition gas was composed of methane, hydrogen and argon with a volume ratio of 1:100:60; the deposition pressure was 2 kPa, and the deposition time was 3 h; the deposition thickness was 6 μm.
- The exposed microcrystalline surface of the prepared diamond was twin crystal (111), and the exposed microcrystalline size was micron level; the structure was columnar crystal, and the carbon content of the sp3 structure in the diamond was 80% (testing method was XPS). SEM image of the diamond is shown in
FIG. 8 , the measured internal stress was 150 MPa, and the hardness was 95 GPa. - Comparison 1
- It is basically the same as Embodiment 1, differing only in that the titanium substrate was directly used as a substrate holder after being polished. The diamond thick film cannot be separated from the substrate, and the preparation of the self-supporting thick film failed.
- Comparison 2
- It is basically the same as Embodiment 1, differing only in that, in Step (2), when preparing the diamond film, only the coupling of arc torch and magnetic resonance was used.
- The prepared diamond film had poor surface uniformity, being thick in the middle while thin in the edges, and large internal stress. Two situations are prone to occur. First, the temperature gradient was too large, the thermal stress was large, and the diamond thick film was broken. 2. In the post-processing process, the diamond thick film was cracked and broken during cutting and processing.
- Comparison 3
- It is basically the same as Embodiment 1, differing only in that, in Step (2), when preparing the diamond film, only the coupling of hot filament and high frequency was used.
- The diamond was of poor quality and contained high sp2 structure, and the growth rate of diamond was slow, and under the same conditions, the thickness of the preparation was 0.9 mm and the growth rate was about 1 μm/h.
- Comparison 4
- It is basically the same as Embodiment 1, differing only in that, processes in Step (3) and Step (4) were not carried out.
- The fracture toughness of the nucleation surface of diamond was very different from that of the growth surface, and the fracture toughness of the growth surface was about 800 MPa, and the fracture toughness of the nucleation surface was 1.1 GPa.
- The embodiments described above are only for illustrating the technical concepts and features of the present disclosure, and are intended to make those skilled in the art being able to understand the present disclosure and thereby implement it, and should not be concluded to limit the protective scope of this disclosure. Any equivalent variations or modifications according to the spirit of the present disclosure should be covered by the protective scope of the present disclosure.
- The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For ranges of value, between the end values of each range, between the end values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new ranges of value, and these ranges of value should be considered as specifically disclosed herein.
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CN112030133B (en) * | 2020-11-06 | 2021-03-23 | 上海征世科技有限公司 | Diamond and preparation method and application thereof |
CN113025990B (en) * | 2021-05-26 | 2021-08-27 | 上海铂世光半导体科技有限公司 | Method for preparing diamond by multi-energy coupling plasma chemical vapor deposition method |
CN114318287B (en) * | 2021-12-23 | 2023-11-03 | 深圳技术大学 | Preparation method of diamond self-supporting film and diamond self-supporting film |
CN115181957B (en) * | 2022-08-25 | 2023-03-17 | 北京爱克瑞特金刚石工具有限公司 | Preparation and application of functional diamond micro-nano powder and complex |
CN115287624A (en) * | 2022-08-29 | 2022-11-04 | 哈尔滨工业大学 | Technology for preparing carbon-based material film based on combined action of bias voltage and laser |
CN115928051A (en) * | 2022-11-29 | 2023-04-07 | 香港中文大学(深圳) | Diamond nanoneedle array light absorption layer and preparation method thereof |
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